Metallocene and process for producing polyolefin using the same

ABSTRACT

A metallocene having an asymmetric ligand which is represented by the formula below and its enantiomer: ##STR1## and a process for producing a polyolefin using the same as a catalyst component. The metallocene and its enantiomer are particularly effective in the production of highly stereospecific polyolefins.

This is a divisional of application Ser. No. 07/982,894 filed Nov. 30,1992.

FIELD OF THE INVENTION

This invention relates to a novel metallocene having a crosslinkedligand having an asymmetric substituent and to a process for producing apolyolefin using the same as a catalyst.

BACKGROUND OF THE INVENTION

Kaminsky's catalyst (metallocene/methylaluminoxane) is widely known as ahomogeneous catalyst for olefin polymerization. This catalyst system ischaracterized by its markedly high activity per unit transition metalthereof. Among metallocenes which are widely known and have beenclassically used is bis(cyclopentadienyl)zirconium dichloride(zirconocene dichloride). Kaminsky et al proposed to copolymerizeethylene and an α-olefin using a catalyst system composed of zirconocenedichloride and methylaluminoxane as disclosed in JP-A-58-19303 (the term"JP-A" as used herein means an "unexamined published Japanese patentapplication"). However, the above catalyst system is disadvantageous inthat it is difficult to obtain a copolymer having a sufficiently highmolecular weight in an industrially advantageous temperature range (50°to 70° C.) and that a large quantity of a comonomer must be charged in apolymerization system in order to obtain a linear low-densitypolyethylene having a desired density.

Ewen et al succeeded in obtaining a high-molecular-weight copolymer in apreferred temperature range (50° to 70° C.) by using a metallocenehaving a substituent on the cyclopentadienyl ligand (see JP-A-60-35007).However, the technique involves a problem from an industrial view pointbecause very expensive methylaluminoxane must be used in a largequantity as a co-catalyst.

Further, Welborn et al proposed to increase the polymerization activityper unit aluminoxane by supporting a metallocene and aluminoxane on aporous inorganic metal oxide (see JP-A-61-296008). The polymerizationactivity reached, however, is not sufficiently high. Besides, thepolymerization activity of the catalyst system is decreasing with timeimmediately after contact between a metallocene and aluminoxane.

Furthermore, Ishihara et al proposed to use a co-catalyst composed ofmethylaluminoxane and other organoaluminum compound in an attempt toincrease the polymerization activity per aluminoxane (see JP-A-60-130604and JP-A-60-260602). However, the effect obtained is not so high asexpected.

It has recently been revealed that use of a Kaminsky's catalyst inpolymerization of α-olefins, chiefly propylene, enables stereospecificpolymerization. For example, it is reported that atactic polypropylene(Macromol. Chem. Rapid Commun., Vol. 4, pp. 417-421 (1983),JP-A-58-19309), isotactic polypropylene (Angew. Chem. Int. Ed. Engl.,Vol. 24, pp. 507-508 (1983), J. Am. Chem. Soc., Vol. 106, p. 6355(1984), J. Am. Chem. Soc., Vol. 109, p. 6544 (1987), Chem. Lett., pp.1853-1856 (1989), JP-A-2-76887), and syndiotactic polypropylene (J. Am.Chem. Soc., Vol. 110, p. 6255 (1988)) can be prepared. The ligandstructure and stereostructure of metallocenes are key points formanifestation of stereospecificity in these polymerization systems.

However, metallocenes which make it possible to produce industriallyimportant isotactic polypropylene are very limited in kind andperformance. For example, ethylenebis(η5-indenyl)zirconium dichloride orethylenebis(η5-tetrahydroindenyl)zirconium dichloride disclosed inJP-A-63-295607 enables production of isotactic polypropylene in thepresence of methylaluminoxane, but the stereospecificity of theisotactic polypropylene obtained in relatively low as about 95% in termsof mm %. Moreover, the resulting polymer has a melting point as low as135°-146° C. because of the occurrence of hydrogen shift polymerizationin the polymer chain, called 1,3-insertion (see Macromol. Chem., RapidComun., Vol. 8, p. 305 (1987)).

JP-A-2-75609 and JP-A-2-75610 describe that an isoblock polymer isobtained by polymerization of propylene in the presence ofindenyl(cyclopentadienyl)(dimethylsilyl)hafnium and methylaluminoxane.The polymer obtained here is a soft polymer having a low melting pointand low stereospecificity (mm %), differing from so-called isotacticpolypropylene of industrial importance.

Ishihara et al. respect production of isotactic polypropylene by the useof (CHI)HfCl₂ (Polymer Preprints, Japan, Vol. 40, p. 265 (1991)), butthe polymer obtained has a very low mm %.

It is reported in JP-A-1-301704, JP-A-1-319489, JP-A-2-76887, and Chem.Lett., pp. 1853-1856 (1989) thatdimethylsilylbis(2,3,5-trimethylcyclopentadienyl)zirconium dichlorideenables production of isotactic polypropylene in the co-presence ofmethylaluminoxane, achieving stereospecificity as high as 99 mm % ormore. It turned out, however, that the polymer chain contains chemicalinversion, which is a polymer chain defect resulting from inversion ofthe direction of monomer insertion and which reduces rigidity of thepolymer (see KOBUNSHI KAKO, Vol. 41, p. 28 (1992)). In addition, thegreatest problem associated with this catalyst system resides in thatthe above zirconium complex includes from the nature of its structuretwo stereoisomers, a racemic modification and a meso form, and that itis only the racemic modification that enables production of highlyisotactic polypropylene. The other isomer, a meso form, catalyzesformation of atactic polypropylene with non-negligible activity.Therefore, the preparation of the complex involves a complicatedpurification step for complete removal of the meso form and thus incursincreased cost.

Collins et al report that isotactic polypropylene is prepared in thepresence of a combination of bis(t-butylcyclopentadienyl)zirconiumdichloride and methylaluminoxane (see Organometallics, Vol. 10, p. 2061(1991)). In this case, too, it is necessary to separating a racemicmixture from an undesired meso form in the preparation of the zirconiumcomplex.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a novel and usefulmetallocene free from the above-mentioned problems associated with theconventional techniques.

Another object of the present invention is to provide an economicalprocess for producing a polyolefin using a metallocene catalyst.

As a result of extensive investigations, the inventors have succeeded insynthesizing novel metallocenes shown below with good efficiency andhave found that the novel metallocenes, which embrace no meso form fromtheir structural nature are extremely useful as a component of acatalyst system for stereospecific polymerization of olefins, thushaving reached the present invention.

The present invention relates to a metallocene represented by formula(I) and its enantiomer: ##STR2## wherein M represents a transition metalselected from Ti, Zr, and Hf; X¹ and X², which may be the same ordifferent, each represents a hydrogen atom, a hydrocarbon groupcontaining from 1 to 10 carbon atoms, an alkylsilyl group, an arylsilylgroup, or a halogen atom; R¹, R², R³, R⁶, and R⁷ each represents ahydrogen atom, a hydrocarbon group containing from 1 to 10 carbon atoms,an alkylsilyl group, or an arylsilyl group, provided that either one ofR¹ and R² is not a hydrogen atom; R⁴ and R⁵ each represents ahydrocarbon group containing from 1 to 10 carbon atoms, an alkylsilylgroup, or an arylsilyl group, or they are connected together to form aring; Y represents a carbon atom, a silicon atom, or a germanium atom;and an represents an integer of from 1 to 3.

The present invention also relates to a process for producing apolyolefin comprising polymerizing an olefin in the presence of ametallocene represented by formula (I) or its enantiomer as a catalyst.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is an Ortep diagram of the metallocene prepared in Example 2obtained by X-ray crystallography.

FIGS. 2, 3 and 4 are the IR spectrum, the ¹ H-NMR spectrum, and the massspectrum, respectively, of the metallocene prepared in Example 2.

DETAILED DESCRIPTION OF THE INVENTION

While the metallocene of the present invention include not only thoserepresented by formula (I) and formulae (II) and (III) described laterbut also their enantiomers, the present invention will be hereinafterexplained with reference to those of formulae (I), (II) and (III)representatively.

On the metallocenes represented by formula (I), those wherein Y is acarbon atom are preferred. More preferred are those wherein Y is acarbon atom; and R⁴ and R⁵ are connected to each other to form a ring,and particularly an indenyl ring, that is, compounds represented byformula (II): ##STR3## wherein M, X¹, X², R¹, R², R³, R⁶, R⁷, and n areas defined above; and Y' represents a carbon atom.

In formulae (I) or (II), M is preferably Zr or Hf. Included in preferredmetallocenes of formula (I) wherein M is Zr are those represented byformula (III): ##STR4## wherein X¹, X², R¹, R², R³, R⁶, and R⁷ aredefined above; and Y' represents a carbon atom.

Metallocenes of formula (III) wherein Zr is replaced with Hf are alsopreferred.

All the compounds represented by formulae (I) through (III) are novelmetallocenes having an asymmetric ligand. In these metallocenes, thesubstituents on each cyclopentadienyl ring at the respective positionsas specified in the formulae (i.e., those represented by R¹ to R⁵) areselected from hydrocarbon groups having from 1 to 10 carbon atoms (e.g.,alkyl, aryl, alkylaryl, and arylalkyl groups), alkylsilyl groups (e.g.,trialkylsilyl groups) and arylsilyl groups (e.g., triarylsilyl groups),and preferably selected from those which are more bulky than a methylgroup, such as a t-butyl group.

While not limiting, the compounds of formula (I) can be synthesizedthrough the following synthetic routes: ##STR5##

In the above scheme, nBt is a normal butyl group, tBu is a t-butylgroup, and THF is tetrahydrofuran.

The reactions shown by schemes (1) and (2) are to introduce asubstituent onto the indene ring or the cyclopentadiene ring and arecarried out by generating an indenyl anion or a cyclopentadienyl anionin a dry THF using an alkali metal, followed by reacting the anion witha halogenated alkyl compound at room temperature to 80° C. The reactionof scheme (3) is to form a fulvene, wherein a cyclopentadienyl anion isgenerated in a dry THF using an alkali metal and is reacted with aketone. The reaction of scheme (4) is to bond the indene compoundobtained by the reaction of scheme (1) and the fulvene compound producedthrough the reactions of schemes (2) and (3), wherein an indenyl anionis generated in a dry THF using an alkali metal and is reacted with thefulvene compound. The reaction of scheme (5) is to form a coordinationcompound of the present invention, wherein a dianion (ligand) of thecompounds obtained by the reaction of scheme (4) is generated in a dryTHF and is reacted with a halogenated metal at a temperature of nothigher than -20° C.

Processes for preparing bis(substituted cyclopentadienyl) bridgedbidendate having a crosslinked structure as shown in scheme (4) areknown, as described in J. Am. Chem. Soc., Vol. 110, pp. 976-978 (1988)and ibid, Vol. 107, pp. 8103-8110 (1985).

Specific examples of the metallocenes according to the present inventionare shown below. In the following nomenclature, the positions ofsubstituents on cyclopentadienyl rings for R¹, R², R³, R⁴ and R⁵ informula (I) are the 3-, 4-, 3'-, 4'- and 5'-positions, respectively.

Examples of the zirconocenes of formula (I) wherein M is zirconium areethylene(4-methylcyclopentadienyl)(3-methylindenyl)zirconium dichloride,ethylene(4-t-butylcyclopentadienyl)(3'-methylindenyl)zirconiumdichloride,ethylene(4-t-butylcyclopentadienyl)(3'-t-butylindenyl)zirconiumdichloride,ethylene(4-methylcyclopentadienyl)(3'-t-butylindenyl)zirconiumdichloride,ethylene(4-methylcyclopentadienyl)(3'-trimethylsilylindenyl)zirconiumdichloride,isopropylidene(4-methylcyclopentadienyl)(3'-methylindenyl)zirconiumdichloride,isopropylidene(4-t-butylcyclopentadienyl)(3-methylindenyl)zirconiumdichloride,isopropylidene(4-t-butylcyclopentadienyl)(3'-t-butylindenyl)zirconiumdichloride,dimethylsilylene(4-methylcyclopentadienyl)(3'-methylindenyl)zirconiumdichloride,dimethylsilylene(4-t-butylcyclopentadienyl)(3'-methylindenyl)zirconiumdichloride,dimethylsilylene(4-t-butylcyclopentadienyl)(3'-t-butylindenyl)zirconiumdichloride,isopropylidene(4-methylcyclopentadienyl)(3',4',5'-trimethylcyclopentadienyl)zirconiumdichloride,isopropylidene(4-t-butylcyclopentadienyl)(3',4',5'-trimethylcyclopentadienyl)zirconiumdichloride,isopropylidene(4-t-butylcyclopentadienyl)(3',4',5'-tri-t-butylcyclopentadienyl)zirconiumdichloride,isopropylidene(4-methylcyclopentadienyl)(3'-methylindenyl)zirconiumdimethyl,isopropylidene(4-t-butylcyclopentadienyl)(3'-methylindenyl)zirconiumdimethyl, andisopropylidene(4-t-butylcyclopentadienyl)(3'-t-butylindenyl)zirconiumdimethyl.

Specific examples of hafnocenes of formula (I) wherein M is hafnium areethylene(4-methylcyclopentadienyl)(3'-methylindenyl)hafnium dichloride,ethylene(4-t-butylcyclopentadienyl)(3'-methylindenyl)hafnium dichloride,ethylene(4-t-butylcyclopentadienyl)(3'-t-butylindenyl)hafniumdichloride, ethylene(4-methylcyclopentadienyl)(3'-t-butylindenyl)hafniumdichloride,ethylene(4-methylcyclopentadienyl)(3'-trimethylsilylindenyl)hafniumdichloride,isopropylidene(4-methylcyclopentadienyl)(3'-methylindenyl)hafniumdichloride,isopropylidene(4-t-butylcyclopentadienyl)(3'-methylindenyl)hafniumdichloride,isopropylidene(3-t-butylcyclopentadienyl)(3'-t-butylindenyl)hafniumdichloride,isopropylidene(4-t-butylcyclopentadienyl)(3'-t-butylindenyl)hafniumdichloride,dimethylsilylene(4-methylcyclopentadienyl)(3'-methylindenyl)hafniumdichloride,dimethylsilylene(4-t-butylcyclopentadienyl)(3'-methylindenyl)hafniumdichloride,dimethylsilylene(4-t-butylcyclopentadienyl)(3'-t-butylindenyl)hafniumdichloride, andisopropylidene(4-methylcyclopentadienyl)(3',4',5'-trimethylcyclopentadienyl)hafniumdichloride.

While these metallocenes respectively include two stereoisomers each ofwhich including respective optical isomers, the ligand has such astructure as providing no meso form which catalyzes production ofatactic polypropylene. It is important that one of the two stereoisomersshould have a considerably low activity or be inactive.

For example, the zirconocene of formula (III) includes two stereoisomersas shown by the following formulas (IV)-A and (IV)-B, each of which is aracemic modification but not a meso form. ##STR6## wherein R¹, R², R³,R⁶, R⁷, X¹, X², and Y' are as defined above.

It has been ascertained that isomer (B) (the metallocenes of formula (I)wherein R¹ is a hydrogen atom) catalyzes production of highly isotaticpolyolefins, whereas isomer (A) (those wherein R² is a hydrogen atom)has no or very low polymerization activity and produces no substantialatactic polyolefin. Therefore, a highly isotactic polyolefin can beproduced even if the metallocene used as a catalyst component is amixture of isomers (A) and (B). That is, there is no need to removeisomer (A) in the preparation of the complex. This is a point greatlydifferent from the conventional metallocenes and is thus characteristicof the present invention.

While other catalyst components to be used in olefin polymerization arenot particularly limited, organoaluminumoxy compounds are preferablyused. Examples of suitable organoaluminumoxy compounds include partialhydrolysis products of organoaluminum compounds (e.g., trialkylaluminumand dialkylaluminum dichloride). In particular, aluminoxane compoundsrepresented by formula (V) or (IV) are particularly preferred. ##STR7##wherein the plurality of R⁸ may be the same or different and eachrepresents a hydrocarbon group such as an alkyl group (e.g., methyl,ethyl, propyl, butyl, or isobutyl, and preferably methyl); and mrepresents an integer of from 4 to 100, preferably 6 or greater, andmore preferably 10 or greater.

Processes for preparing these aluminoxane compounds are well known asdescribed in H. Sinn, Transition Metals and Organometallics as Catalystsfor Olefin Polymerization, p.257, ed. by W. Kaminsky and H. Sinn,Springer Verlag, Berlin (1988). For example, they may be obtained byadding a trialkylaluminum to a suspension of a crystal water-containingsalt (e.g., copper sulfate hydrate or aluminum sulfate hydrate) in ahydrocarbon solvent.

Olefins which may be polymerized according to the process of the presentinvention include olefins, cyclic olefins and dienes, such as propylene,1-butene, 2-butene, 1-pentene, 4-methyl-1-pentene, cyclopentene,norbornene, cyclopentadiene, butadiene, 1,5-hexadiene, and1,4-hexadiene. These olefins may be used either individually or as amixture of two or more thereof. The present invention is particularlyadvantageous in the polymerization of olefins having 3 or more carbonatoms.

The polymerization may be carried out by any of liquid phasepolymerization, slurry polymerization and gas phase polymerization.Solvents to be used in liquid phase polymerization include hydrocarbonsolvents capable of dissolving both the metallocene andorganoaluminumoxy compound, such as aromatic hydrocarbons, e.g.,benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene,butylbenzene, mesitylene, and chlorobenzene, with toluene and xylenebeing preferred.

The metallocene and organoaluminumoxy compound may be supplied to areaction system either separately or in the form of a mixture thereof.The metallocene of the present invention may also be used as beingsupported on a carrier, such has silica, alumina, or magnesium chloride.

The concentration of the metallocene having the catalytic activity(i.e., isomer (B)) in a reaction solution (including a solvent) of thereaction system is not particularly limited, and it is preferably usedin an amount of from 10⁻¹⁰ to 10⁻³ mol/l, with the Al/M molar ratio (M:Ti, Zr and Nf) being 10 or more, and particularly 100 or more.

While the olefin pressure of the reaction system and the polymerizationtemperature are not critical, it is preferred to carry out the reactionat a temperature of from -30° to 200° C., more preferably from 0° to 80°C., and most preferably from 50° to 70° C., at an olefin pressure offrom normal pressure to 50 kg/cm². Molecular weight control during thepolymerization can be effected by any known means, such as properselection of a reaction temperature or hydrogen introduction.

Copolymerization of ethylene and an α-olefin is a preferred embodimentof the present invention. In this embodiment, the metallocene andorganoaluminumoxy compound are employed in the form of a solid catalystsupported on an inorganic oxide carrier together with an organoaluminumcompound (other than organoaluminumoxy compounds) as a co-catalystthereby to exhibit extremely effective catalyzing performance.

While not limiting, the inorganic oxide as a carrier includes silica,alumina, magnesia, aluminosilicate, boron oxide, and calcium oxide. Theabove inorganic oxide carrier having been sintered at a high temperatureare treated with an organoaluminum compound is preferred.

While not limiting, the amounts of the metallocene and theorganoaluminumoxy compound to be supported on the inorganic oxidecarrier preferably range from 0.05 to 10% by weight and from 0.01 to 70%by weight, and more preferably from 0.5 to 5% by weight and from 0.01 to30% by weight, respectively, based on the carrier.

While not limiting, the organoaluminum compound which can be used as aco-catalyst preferably includes trialkylaluminum compounds, andparticularly triisobutylaluminum, trimethylaluminum, andtrioctylaluminum. The concentration of the organoaluminum compound in areaction solution of the reaction system is usually from 0.001 to 1mmol/l in terms of aluminum. The organoaluminum compound may be premixedwith the metallocene-carried solid catalyst immediately beforepolymerization.

α-Olefins which are copolymerized with ethylene according to theabove-mentioned preferred embodiment of the present invention includeolefins, cyclic olefins and dienes, such as propylene, 1-butene,1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 4-methyl-1-pentene,cyclopentene, cyclopentadiene, butadiene, 1,5-hexadiene, 1,4-hexadiene,and 1,4-pentadiene. These comonomers may be used either individually orin combination of two or more thereof.

The molar ratio of ethylene to α-olefin in the ethylene copolymer is notparticularly limited but preferably ranges from 0.5/1 to 10,000/1,particularly from 10/1 to 1000/1. The possible lowest density that theresulting copolymer may have is 0.80. Ethylene copolymers having adensity of from 0.89 to 0.94 are preferably used.

The copolymerization may be carried out by any of liquid phasepolymerization, slurry polymerization and gas phase polymerization, andpreferably slurry polymerization in isobutane or gas phasepolymerization. Multi-stage polymerization is also feasible. Sizecontrol of the ethylene copolymer may be effected by prepolymerizationof the olefins. While the ethylene pressure of the reaction system isnot particularly limited, it is preferably from normal pressure to 1000Kg/cm² and more preferably from 1 to 40 Kg/cm².

According to the above-described preferred embodiment, the catalystsystem exhibits high activity per unit co-catalyst and undergoes nochange in activity with time, and an ethylene-α-olefin copolymer havinga low melting point, high transparency, and a narrow compositiondistribution can be produced.

The present invention is now illustrated in greater detail withreference to Examples, but it should be understood that the presentinvention is not deemed to be limited thereto.

An NMR analysis on the polyolefin produced was conducted with "EX-400"manufactured by Japan Electron Optics Laboratory Co., Ltd.Stereospecificity of the polyolefins obtained was determined from the ¹³C-NMR spectrum and evaluated in terms of intensity ratio of mm, mr, andrr signals. The proportion of triad unit in the polyolefin molecularchain is given in terms of "mm %". Absorption peaks of the NMR spectrumwere assigned according to Macromolecules, Vol. 8, p.687 (1975).

The molecular weight of the polyolefins obtained was estimated throughgel-permeation chromatography using "Waters-150C" and a column "Shodex".

Physical properties of the ethylene-α-olefin copolymers obtained weremeasured through an FT-IR analysis using "Perkin-Elmer 1720X" anddifferential thermal analysis using "Perkin-Elmer DSC-7".

The molecular weight of the ethylene-α-olefin copolymers obtained wasevaluated in terms of a melt flow rate (hereinafter abbreviated as MFR)as measured at 190° C. under a load of 2.16 kg in accordance with JISK-6760. High-load melt index (hereinafter abbreviated as HLMI) of thecopolymers was measured under a load of 21.6 kg.

The ratio of an α-olefin in the ethylene-α-olefin copolymers(hereinafter abbreviated as SCB) was expressed by the number of branchesin the polymer main chain as determined by the FT-IR analysis.Specifically, the number of branches per 1000 carbon atoms in thepolymer main chain was calculated from a ratio of the peak height at1380 cm⁻¹ of the IR spectrum of a sample copolymer to that at 4250 cm⁻¹of the IR spectrum of polyethylene having no branching.

EXAMPLE 1 Preparation ofIsopropylidene(4-methylcyclopentadienyl)(3'-t-butylindenyl)zirconiumDichloride

All the reactions were carried out in an inert gas atmosphere, and thereactor used had been dried beforehand.

In a 300 ml glass-made reactor was charged 100 ml of dry tetrahydrofuran(THF), and 3 g ofdimethyl(4-methylcyclopentadienyl)(3'-t-butylindenyl)methane wasdissolved therein. To the solution was added 15 ml of a 1.6 mol/l hexanesolution of n-butyl lithium under cooling with ice. After the mixturewas allowed to react at room temperature for 1 hour, THF was removed bydistillation under reduced pressure. To the residue was added 50 ml ofmethylene chloride while cooling. A suspension of 2.63 g of zirconiumtetrachloride in 50 ml of methylene chloride, which had been prepared ina separate flask, was cooled, and the above-prepared suspension ofdimethyl(4-methylcyclopentadienyl)(3'-t-butylindenyl)methane lithiumsalt was added thereto while being cooled through a cannula, followed byreacting at room temperature for 2 hours. Lithium chloride thus formedwas removed, and the residual solution was concentrated, followed byrecrystallization from toluene several times, whereby 0.8 g of thetilted complex was obtained as a crystal.

Elementary Analysis for C₂₂ H₂₆ ZrCl₂ : Calcd. (%): C, 58.39; H 5.79.Found (%): C, 58.30; H 5.77.

Polymerization

In a 1.5 l SUS-made autoclave having been thoroughly purged withnitrogen were successively charged 300 ml of purified toluene, 15 ml ofa toluene solution containing 2.7 mol/l (in terms of aluminum) ofmethylaluminoxane (produced by TOSO AKUZO CO., LTD.), and 0.02 mmol ofthe above-prepared zirconocene, followed by cooling to 3° C. Then, 2mols of propylene was poured thereinto, and polymerization was conductedfor 1 hour. The catalyst components were decomposed with methanol, andthe residue was dried to recover 37 g of highly isotactic polypropylene.

mm %: 99.1%.

Molecular Weight: 102,000.

Melting Point: 162° C.

EXAMPLE 2 Preparation ofIsopropylidene(4-t-butylcyclopentadienyl)(3'-t-butylindenyl)zirconiumDichloride

All the following reactions were carried out in an inert gas atmosphere,and the reactor used had been dried beforehand.

In a 300 ml glass-made reactor was charged 100 ml of dry THF, and 3 g ofdimethyl(4-butylcyclopentadienyl)(3'-t-butylindenyl)methane wasdissolved therein. To the solution was added 15 ml of a 1.6 mol/l hexanesolution of n-butyl lithium under cooling with ice. After the mixturewas allowed to react at room temperature for 1 hour, THF was removed bydistillation under reduced pressure. To the residue was added 50 ml ofmethylene chloride while cooling. A suspension of 2.63 g of zirconiumtetrachloride in 50 ml of methylene chloride, which has been prepared ina separate flask, was cooled, and the above-prepared suspension ofdimethyl(4-butylcyclopentadienyl)(3'-t-butylindenyl)methane lithium saltwas added thereto while being cooled through a cannula, followed byreacting at room temperature for 2 hours. Lithium chloride thus formedwas removed, and the residual solution was concentrated, followed byrecrystallization from toluene several times, whereby 0.3 g of thetilted zirconocene was obtained as an orange crystal.

Elementary Analysis for C₂₅ H₃₂ ZrCl₂ : Calcd. (%): C 60.78; H 6.53.Found (%): C 60.81; H 6.48.

The Ortep diagram of the crystal obtained by X-ray crystallography isshown in FIG. 1.

The IR spectrum of the crystal was measured according to the KBr methodusing an IR analyzer "Perkin-Elmer 5150" and it is shown in FIG. 2. The¹ H-NMR spectrum of the crystal (in CDCl₃) was also measured using theNMR analyzer "EX-400" and shown in FIG. 3. Further, the mass spectrumwas measured according to the direct introduction method using a massspectrometer "JMS-AX500" manufactured by Japan Electron OpticsLaboratory Co., Ltd. and it is shown in FIG. 4.

Polymerization

In a 1.5 l SUS-made autoclave having been thoroughly purged withnitrogen were successively charged 300 ml of purified toluene, 15 ml ofa toluene solution containing 2.7 mol/l (in terms of aluminum) ofmethylaluminoxane (produced by TOSO AKUZO CO., LTD.), and 0.02 mmol ofthe above-prepared zirconocene, following by cooling to 3° C. Then, 2mols of propylene was poured thereinto, and polymerization was conductedfor 1 hour. The catalyst components were decomposed with methanol, andthe residue was dried to recover 40 g of highly isotactic polypropylene.

mm %: 99.6%.

Molecular Weight: 160,000.

Melting Point: 164° C.

EXAMPLE 3 Preparation ofIsopropylidene(4-t-butylcyclopentadienyl)(3'-t-butylindenyl)hafniumDichloride

All the reactions were carried out in an inert gas atmosphere, and thereactor used has been dried beforehand.

In a 300 ml glass-made reactor was charged 100 ml of dry THF, and 3 g ofdimethyl(4-t-butylcyclopentadienyl)(3'-t-butylindenyl)methane wasdissolved therein. To the solution was added 15 ml of a 1.6 mol/l hexanesolution of n-butyl lithium under cooling with ice. After the mixturewas allowed to react at room temperature for 1 hour, THF was removed bydistillation under reduced pressure. To the residue was added 50 ml ofmethylene chloride while cooling. A suspension of 3.0 g of hafniumtetrachloride in 50 ml of methylene chloride, which had been prepared ina separate flask, was cooled, and the above-prepared suspension ofdimethyl(4-t-butylcyclopentadienyl)(3'-t-butylindenyl)methane lithiumsalt was added thereto while being cooled through a cannula, followed byreacting at room temperature for 2 hours. Lithium chloride thus formedwas removed, and the residual solution was concentrated, followed byrecrystallization from toluene several times, whereby 0.35 g of thetitled complex was obtained as a crystal.

Elementary Analysis for C₂₅ H₃₂ HfCl₂ : Calcd. (%): C 51.60; H 5.54.Found (%): C 51.42; H 5.32.

Polymerization

In a 1.5 l SUS-made autoclave having been thoroughly purged withnitrogen were successively charged 300 ml of purified toluene, 15 ml ofa toluene solution containing 2.7 mol/l (in terms of aluminum) ofmethylaluminoxane (produced by TOSO AKUZO CO., LTD.), and 0.02 mmol ofthe above-prepared hafnocene, followed by cooling to 3° C. Then, 2 molsof propylene was poured thereinto, and polymerization was conducted for1 hour. The catalyst components were decomposed with methanol, and theresidue was dried to recover 35 g of highly isotactic polypropylene.

mm %: 99.6%.

Molecular Weight: 260,000.

COMPARATIVE EXAMPLE 1

Propylene was polymerized in the same manner as in Example 1, except forreplacingisopropylidene(4-methylcyclopentadienyl)(3'-t-butylindenyl)zirconiumdichloride with ethylenebis(indenyl)zirconium dichloride. There wasobtained 40 g of isotactic polypropylene.

mm %: 94.2%

Molecular Weight: 65,000.

COMPARATIVE EXAMPLE 2

Propylene was polymerized in the same manner as in Example 1, except forreplacingisopropylidene(4-methylcyclopentadienyl)(3'-t-butylindenyl)zirconiumdichloride withdimethylsilylbis(2,3,5-trimethylcyclopentadienyl)zirconium dichloride (a100% racemic modification). There was obtained 23 g of isotacticpolypropylene.

mm %: 98.3%.

Molecular Weight: 99,800.

The occurrence of chemical inversion in the polypropylene obtained inExamples 1 to 3 and Comparative Examples 1 and 2 was determined by a ¹³C-NMR analysis according to a known method described in literature(Macromolecules, Vol. 21, p. 617 (1988)). The results obtained are shownin Table 1 below.

                  TABLE 1                                                         ______________________________________                                        Example    The Number of Chemical                                             No.        Inversions per 1000 Monomer Units                                  ______________________________________                                        Example 1  3.6                                                                Example 2  2.1                                                                Example 3  2.0                                                                Compara.   4.6                                                                Example 1                                                                     Compara.   4.0                                                                Example 2                                                                     ______________________________________                                    

EXAMPLE 4

Propylene was polymerized in the same manner as in Example 2, except forreplacingisopropylidene(4-t-butylcyclopentadienyl)(3'-t-butylindenyl)zirconiumdichloride with a mixture thereof with its stereoisomer (purity: 60%).There was obtained 25 g of highly isotatic polypropylene.

mm %: 99.6%.

COMPARATIVE EXAMPLE 3

Propylene was polymerized in the same manner as in Example 2, except forreplacingisopropylidene(4-t-butylcyclopentadienyl)(3'-t-butylindenyl)zirconiumdichloride with an isomeric mixture ofdimethylsilylbis(2,3,5-trimethylcyclopentadienyl)zirconium dichloride(racemic modification/meso form: 60%). There was obtained 30 g of amixture of isotactic polypropylene and atactic polypropylene.

mm %: 78.5%.

EXAMPLE 5

In a 200 ml flask having been purged with argon was charged 100 ml ofdehydrated toluene, and 7 ml of a 2.65 mol/l toluene solution ofmethylaluminoxane and a toluene solution of 0.02 mmol ofisopropylidene(4-t-butylcyclopentadienyl)(3'-t-butylindenyl)zirconiumdichloride were added thereto, followed by stirring at 40° C. for 10minutes. To the solution was added 20 ml of 4-methylpentene-1, andpolymerization was conducted at 40° C. for 3 hours to obtain 12.7 g ofhighly isotactic poly(4-methylpentene-1).

COMPARATIVE EXAMPLE 4

4-Methylpentene-1 was polymerized in the same manner as in Example 5,except for replacingisopropylidene(4-t-butylcyclopentadienyl)(3'-t-butylindenyl)zirconiumdichloride with zirconocene dichloride, to obtain 9 g of atacticpoly(4-methylpentene-1).

EXAMPLE 6

Polymerization reaction was carried out in the same manner as in Example5, except for replacing 4-methylpentene-1 to be polymerized with 20 mlof 1,5-hexadiene, to obtain 16 g of a cyclized polymer.

EXAMPLE 7

Polymerization reaction was carried out in the same manner as in Example5, except for replacing 4-methylpentene-1 to be polymerized with 20 mlof 1,4-hexadiene, to obtain 9 g of a polymer.

EXAMPLE 8 Preparation of Catalyst Process A

In a 100 ml flask having been purged with nitrogen was charged 2 g ofsilica ("DAVISON 955"; sintered at 600° C. for 8 hours), and 20 ml ofdehydrated toluene was added thereto to prepare a slurry. To the slurrywas added 0.3 ml of a 2.5 mol/l toluene solution of methylaluminoxane(produced by TOSO AKUZO CO., LTD.), followed by allowing the mixture toreact at room temperature for 1 hour. The solvent was removed bydistillation under reduced pressure. To the residue was added 7.5 ml ofa 1 mmol/l hexane solution ofisopropylidene(4-t-butylcyclopentadienyl)(3'-t-butylindenyl)zirconiumdichloride as prepared in Example 2, and the mixture was allowed toreact for 1 hour, followed by drying under reduced pressure to obtain asolid catalyst (designated A type).

Copolymerization

In a 1.5 l SUS-made autoclave having been thoroughly purged withnitrogen were charged 70 mg of the above-prepared A type catalyst, 3.5ml of a 0.5 mol/l hexane solution of triisobutylaluminum, and 800 ml ofisobutane. To the mixture was introduced ethylene and 27 g of 1-hexene,and polymerization was conducted under an ethylene pressure of 3 kg/cm²at 70° C. After 1 hour, the reaction system was purged to cease thepolymerization.

EXAMPLES 9 AND 10 Preparation of Catalyst

Process B

A solid catalyst component was prepared in the same manner as in ProcessA described in Example 8, except for using silica having been treated inhexane with 0.6 mmol of triethylaluminoxane and the complex as shown inTable 2 below (designated B type).

Copolymerization

Ethylene and 1-hexene were copolymerized in the same manner as inExample 8, except for using the above-prepared B type catalyst.

EXAMPLES 11 AND 12

Ethylene and 1-hexene were copolymerized in the same manner as inExample 8 or 9, except for using A type or B type catalyst prepared byusing alumina as a carrier and changing the amounts of the complex andmethylaluminoxane as shown in Table 2 below.

EXAMPLE 13

Ethylene and 1-hexene were copolymerized in the same manner as inExample 8, except for replacing silica as a carrier with magnesia andchanging the amounts of methylaluminoxane and the complex catalyst asshown in Table 2 below.

EXAMPLE 14

Ethylene and 1-hexene were copolymerized in the same manner as inExample 8, except for replacing silica as a carrier with boron oxide andchanging the amounts of methylaluminoxane and the complex catalyst asshown in Table 2 below.

Each of the ethylene/1-hexene copolymers prepared in Examples 8 to 14was press molded at 190° C. The resulting molded article was excellentin transparency in every case.

COMPARATIVE EXAMPLE 5

Ethylene and 1-hexene were copolymerized in the same manner as inExample 8, except for replacing the catalyst used in Example 8 withzirconocene dichloride having the composition shown in Table 2 below(prepared by Process A).

Each of the catalysts used in Examples 8 to 14 and Comparative Example 5was evaluated for activity in terms of specific rate (RSP) calculated bydividing an amount (g) of polymers produced with 1 g of the catalystcomponent for 1 hour, by the ethylene pressure (atm) in the reactionsystem. Further, physical properties of each of the ethylene/1-hexenecopolymers obtained in these Examples were measured. The resultsobtained are shown in Table 2.

It is seen from the results that linear low-density ethylene copolymershaving a high molecular weight and a mono-model melting point can beobtained by the use of the metallocene of the present invention.

                                      TABLE 2                                     __________________________________________________________________________                Composition of Solid                                                                         Catalyst                                                                            Catalyst                                     Process     Catalyst (reduced                                                                            Activity                                                                            Activity                                     of          to gram/gram-carrier)                                                                        A*.sup.2                                                                            B*.sup.3      Melting                        Example                                                                             Catalyst                                                                            Carrier                                                                            Complex                                                                            MAO*.sup.1                                                                         (g/g · hr ·                                                       (g/g · hr ·                                                               Point                          No.   Preparation                                                                         (g)  (g)  (g)  atm)  atm)  MFR HLMI                                                                              (°C.)                                                                       SCB                       __________________________________________________________________________    Example 8                                                                           A     silica                                                                             0.043                                                                              0.5  6600  560   n.f.*.sup.4                                                                       0.045                                                                             120  18                                    1                                                                 Example 9                                                                           B     silica                                                                             0.017                                                                              0.1  5000  470   n.f.                                                                              0.021                                                                             118  19                                    1                                                                 Example                                                                             B     silica                                                                             0.034                                                                              0.2  4080  698   n.f.                                                                              0.028                                                                             115  21                        10          1                                                                 Example                                                                             A     alumina                                                                            0.034                                                                              0.2  1740  290   n.f.                                                                              0.016                                                                             114  21                        11          1                                                                 Example                                                                             B     alumina                                                                            0.034                                                                              0.2  2220  380   n.f.                                                                              0.035                                                                             117  20                        12          1                                                                 Example                                                                             A     magnesia                                                                           0.034                                                                              0.2  1050  170   n.f.                                                                              0.041                                                                             117  19                        13          1                                                                 Example                                                                             A     boron                                                                              0.034                                                                              0.2  1900  360   n.f.                                                                              0.049                                                                             116  19                        14          oxide 1                                                           Compara.                                                                            A     silica                                                                             0.034                                                                              0.2   617  102   75.4                                                                              --  123  10                        Example 5   1                                                                 __________________________________________________________________________     Note:                                                                         *.sup.1 Methylaluminoxane                                                     *.sup.2 RSP (per gram of the complex)                                         *.sup.3 RSP (per gram of methylaluminoxane)                                   *.sup.4 The sample did not melt to flow.                                 

EXAMPLE 15

The catalyst used in Example 8 was preserved in an ampule containingnitrogen for a long time, and the change in activity in terms of RSP(per gram of methylaluminoxane) was observed with time. The resultsobtained are shown in Table 3 below.

COMPARATIVE EXAMPLE 6

The change in activity of the catalyst used in Comparative Example 5 wasobserved with time in the same manner as in Example 15. The resultsobtained are shown in Table 3 below.

                  TABLE 3                                                         ______________________________________                                        RSP                                                                           (per gram of Methylaluminoxane) (g/g · hr · atm)                    On The       After      After                                         Example Day of       4 Days'    10 Days'                                      No.     Preparation  Preservation                                                                             Preservation                                  ______________________________________                                        Example 560          550        380                                           15                                                                            Compara.                                                                              102           40         8                                            Example                                                                       ______________________________________                                    

It is seen from the results in Table 3 that the catalyst of the presentinvention exhibits good stability.

EXAMPLE 16

Ethylene and 1-hexene were copolymerized in the same manner as inExample 8, except for conducting polymerization in the co-presence ofhydrogen. The resulting ethylene copolymer has an MFR of 2.3.

According to the present invention, the asymmetric metallocene offormula (I) can be used as a catalyst component for olefinpolymerization without requiring any treatment for separation of anisomer, such as a high technique of fractional crystallization, toproduce an industrially valuable poly-α-olefin with very highstereospecificity and reduced chemical inversion in its polymer chain atgood efficiency.

Further, by using a solid catalyst composed of the asymmetricmetallocene of the present invention and an organoaluminumoxy compoundas supported on an inorganic oxide carrier in combination with anorganoaluminum component as a co-catalyst, an ethylene-α-olefincopolymer having a high molecular weight and a low and mon-modal meltingpoint (this means that the copolymer has a narrow compositiondistribution) can be obtained with good activity per unitorganoaluminumoxy component.

While the invention has been described in detail and with reference tospecific examples thereof, it will be apparent to one skilled in the artthat various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A process for producing a polyolefin comprisingusing, as a catalyst component, a metallocene represented by formula (I)or its enantiomer: ##STR8## wherein M represents a transition metalselected from Ti, Zr, and Hf, X¹ and X², which may be the same ordifferent, each represents a hydrogen atom, a hydrocarbon groupcontaining from 1 to 10 carbon atoms, an alkylsilyl group, an arylsilylgroup, or a halogen atom; R¹, R², R³, R⁶, and R⁷ each represents ahydrogen atom, a hydrocarbon group containing from 1 to 10 carbon atoms,an alkylsilyl group, or an arylsilyl group, provided that either one ofR¹ and R² is not a hydrogen atom; R⁴ and R⁵ each represents ahydrocarbon group containing from 1 to 10 carbon atoms, an alkylsilylgroup, or an arylsilyl group, or they are connected together to form aring; Y represents a carbon atom, a silicon atom, or a germanium atom;and n represents an integer of from 1 to
 3. 2. The process as claimed inclaim 1, wherein said metallocene or its enantiomer is used incombination with an organoaluminumoxy compound.
 3. The process asclaimed in claim 2, wherein said organoaluminumoxy compound ismethylaluminoxane.
 4. The process as claimed in claim 1, wherein Y informula (I) is a carbon atom.
 5. The process as claimed in claim 1,wherein said metallocene or its enantiomer is a compound represented byformula (II) or its enantiomer: ##STR9## wherein M, X¹, X², R¹, R², R³,R⁶, R⁷ and n are as defined in formula (I); and Y' represents a carbonatom.
 6. The process as claimed in claim 5, wherein M is hafnium.
 7. Theprocess as claimed in claim 1, wherein said metallocene or itsenantiomer is a zirconocene represented by formula (III) or itsenantiomer: ##STR10## wherein X¹, X², R¹, R², R³, R⁶, and R⁷ are asdefined in formula (I), and Y' represents a carbon atom.
 8. The processas claimed in claim 1, wherein R¹ represents a hydrogen atom.
 9. Aprocess for producing a copolymer of ethylene and an α-olefin comprisingusing a solid catalyst obtained by supporting (a) a metallocenerepresented by formula (I) or its enantiomer: ##STR11## wherein Mrepresents a transition metal selected from ti, Zr, and Hf; X¹ and X²,which may be the same or different, each represents a hydrogen atom, ahydrocarbon group containing from 1 to 10 carbon atoms, an alkylsilylgroup, an arylsilyl group, or a halogen atom; R¹, R², R³, R⁶, and R⁷each represents a hydrogen atom, a hydrocarbon group containing from 1to 10 carbon atoms, an alkylsilyl group, or an arylsilyl group, providedthat either one of R¹ and R² is not a hydrogen atom; R⁴ and R⁵ eachrepresents a hydrocarbon group containing from 1 to 10 carbon atoms, analkylsilyl group, or an arylsilyl group, or they are connected togetherto form a ring; Y represents a carbon atom, a silicon atom, or agermanium atom; and n represents an integer of from 1 to 3, and (b) anorganoaluminumoxy compound on (c) an inorganic oxide carrier incombination with, as a co-catalyst, an organoaluminum compound.
 10. Theprocess as claimed in claim 9, wherein said metallocene or itsenantiomer (a) is a metallocene represented by formula (II) or itsenantiomer: ##STR12## wherein M, X¹, X², R¹, R², R³, R⁶, R⁷, and n areas defined in formula (I); and Y' represents a carbon atom, saidorganoaluminumoxy compound (b) is methylaluminoxane, and said inorganicoxide carrier (c) is silica or alumina.
 11. The process as defined inclaim 9, wherein said inorganic oxide carrier (c) is silica or aluminahaving been treated with an organoaluminum compound.